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EP0371406A1 - Oxyalkylated quaternary ammonium compounds, processes for production thereof, and plant growth regulating compositions containing said compounds - Google Patents

Oxyalkylated quaternary ammonium compounds, processes for production thereof, and plant growth regulating compositions containing said compounds Download PDF

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Publication number
EP0371406A1
EP0371406A1 EP89121723A EP89121723A EP0371406A1 EP 0371406 A1 EP0371406 A1 EP 0371406A1 EP 89121723 A EP89121723 A EP 89121723A EP 89121723 A EP89121723 A EP 89121723A EP 0371406 A1 EP0371406 A1 EP 0371406A1
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EP
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Prior art keywords
quaternary ammonium
ammonium compound
group
general formula
compound
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Application number
EP89121723A
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German (de)
French (fr)
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EP0371406B1 (en
Inventor
Akira Taniuchi
Hironori Kataoka
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DKS Co Ltd
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Dai Ichi Kogyo Seiyaku Co Ltd
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Priority claimed from JP30147588A external-priority patent/JP2881443B2/en
Priority claimed from JP30147688A external-priority patent/JPH02145552A/en
Priority claimed from JP30147788A external-priority patent/JPH02145559A/en
Priority claimed from JP8089489A external-priority patent/JPH02258748A/en
Priority claimed from JP21463489A external-priority patent/JPH0377851A/en
Application filed by Dai Ichi Kogyo Seiyaku Co Ltd filed Critical Dai Ichi Kogyo Seiyaku Co Ltd
Publication of EP0371406A1 publication Critical patent/EP0371406A1/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/11—Esters of phosphoric acids with hydroxyalkyl compounds without further substituents on alkyl
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A01N33/02—Amines; Quaternary ammonium compounds
    • A01N33/12—Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
    • C07C215/02—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C215/40—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton with quaternised nitrogen atoms bound to carbon atoms of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C229/06—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton
    • C07C229/10—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
    • C07C229/12—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings to carbon atoms of acyclic carbon skeletons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C229/24—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having more than one carboxyl group bound to the carbon skeleton, e.g. aspartic acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
    • C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C309/13—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton
    • C07C309/14—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton containing amino groups bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C309/45—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton
    • C07C309/46—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton having the sulfo groups bound to carbon atoms of non-condensed six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
    • C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C323/57—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being further substituted by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C323/58—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being further substituted by nitrogen atoms, not being part of nitro or nitroso groups with amino groups bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/091—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl

Definitions

  • the present invention relates to novel oxyalkyl­ated quaternary ammonium compounds, processes for production thereof and plant growth regulating composi­tions containing said compounds.
  • the novel oxyalkylated quaternary ammonium com­pound of the present invention consists of a cationic group of the general formula wherein R1 means an C6 ⁇ 22 alkyl or alkenyl group, R2 means an C1 ⁇ 4 alkyl or hydroxyalkyl group and R3 and R4 independently mean (BO) x H where B is an C1 ⁇ 4 alkylene group and x means a whole or fractional number of 1 to 5 and an anionic group selected from the class consisting of carboxylic acid residues, amino­sulfonic acid residues and phosphate ester residues.
  • the processes for producing said oxyalkylated quaternary ammonium compound in accordance with the invention generally comprise reacting a quaternary ammonium compound of the general formula wherein R1, R2, R3 and R4 are respectively as defined above and Y means Cl, Br, I or F with at least one member of the class consisting of alkali metal salts of carboxylic acids, alkaline earth metal salts of carboxylic acids, alkali metal salts of aminosulfonic acids, alkaline earth metal salts of aminosulfonic acids, alkali metal salts of phosphoric acid esters and alkaline earth metal salts of phosphoric acid esters in a solvent, either in the presence of a small amount of said novel oxyalkylated quaternary ammonium compound or in the absence thereof.
  • the solvent mentioned just above is preferably selected from the class consisting of straight-chain or branched C1 ⁇ 6 alcohols, methyl ethyl ketone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, dioxane, ethyl acetate and cyclo­hexanol, and these solvents may be used singly or in combination.
  • the plant growth regulating composition of the present invention contains the above-mentioned novel oxyalkylated quaternary ammonium compound.
  • the reaction for production of the novel oxyalkyl­ated quaternary ammonium compound is generally con­ducted at 30 to 100°C for about 3 to 24 hours.
  • the byproduced alkali metal halide or alkaline earth metal halide is filtered off and the solvent is removed from the filtrate to isolate the object compound.
  • the residue on evaporation of the solvent is dissolved in a solvent, such as a straight-chain or branched C1 ⁇ 6 alcohol, acetone, methyl ethyl ketone, n-hexane, cyclohexane, benzene, toluene, xylene or the like or an appropriate mixture of such solvents and the solution is filtered. The filtrate is then concen­trated or cooled to recover purified materials.
  • a solvent such as a straight-chain or branched C1 ⁇ 6 alcohol, acetone, methyl ethyl ketone, n-hexane, cyclohexane, benzene, toluene, xylene or the like or an appropriate mixture of such solvents and the solution is filtered. The filtrate is then concen­trated or cooled to recover purified materials.
  • Preferred examples of the solvent to be used in the production processes of the present invention include, as aforesaid, straight-chain or branched C1 ⁇ 6 alcohols, ethyl acetate, dioxane, methyl ethyl ketone, cyclohexanol, dimethyl sulfoxide, dimethylform­amide and dimethylacetamide, although other solvents may likewise be employed unless they interfere with the intended reaction.
  • the preferred amount of the solvent is one to 10-fold by weight relative to the combined weight of said compound (2) and said alkali metal salt or alkaline earth metal salt.
  • the reaction can also be conducted in the presence of not more than about 10 weight percent of the novel oxyalkylated quaternary ammonium compound of the invention relative to the above-mentioned combined weight.
  • an alkali iodide may be added in a proportion of not more than 10 weight percent of com­pound (2).
  • nitrogen gas may be intro­duced into the reaction system at a low flow rate.
  • a preferred class of the novel oxyalkylated quaternary ammonium compound according to the present invention can be written as follows. wherein R1, R2, R3 and R4 are respectively as defined hereinbefore, A ⁇ is R5NHR6COO ⁇ , where R5 means a hydrogen atom, an C1 ⁇ 4 alkyl group, NH2CH2(CH2)3-, or HSCH2-, and R6 means CH, CH2 or an aromatic group.
  • the process for producing the above compound (3) comprises reacting a quaternary ammonium compound of general formula (2) with a compound of general formula (4) R5NHR6COOD (4), a compound of general formula (5) or a compound of general formula (6) wherein R5 and R6 are as defined hereinbefore and D means an alkali metal atom or an alkaline earth metal atom in a solvent, such as those mentioned hereinbe­fore, either in the presence of a small amount of the novel oxyalkylated quaternary ammonium compound (3) or in the absence thereof.
  • Examples of compound (2) include, among others, octylmethyldihydroxyethylammonium chloride, lauryl­methyldihydroxyethylammonium bromide, oleylethyldi­hydroxyethylammonium iodide, stearylmethyldihydroxypro­pylammonium chloride, hexylethyldihydroxybutylammonium bromide, oleyltrihydroxyethylammonium chloride, lauryl­ trihydroxyethylammonium chloride, stearyltrihydroxy­ethylammonium chloride, oleyltrihydroxyethylammonium bromide, octyldihydroxyethylhydroxypropylammonium chloride, oleylmethyldihydroxyethoxyethylammonium chloride and so on.
  • Examples of the compound of general formula (4), (5), or (6) include alkali metal or alkaline earth metal salts of amino acids such as glycine potassium salt, sarcosine sodium salt, alanine potassium salt, leucine potassium salt, valine sodium salt, cysteine sodium salt, potasssium indoleacetate, potassium pyrrolidonecarboxylate, serine calcium salt, methionine potassium salt, proline potassium salt, tryptophan sodium salt, lysine calcium salt, potassium aminobenzo­ate and so on.
  • amino acids such as glycine potassium salt, sarcosine sodium salt, alanine potassium salt, leucine potassium salt, valine sodium salt, cysteine sodium salt, potasssium indoleacetate, potassium pyrrolidonecarboxylate, serine calcium salt, methionine potassium salt, proline potassium salt, tryptophan sodium salt, lysine calcium salt, potassium aminobenzo­ate and so on.
  • the preferred ratio of compound (4), (5) or (6) to compound (2) is 1 to 1.5 moles of (4), (5) or (6) to each mole of (2).
  • R1, R2, R3 and R4 are respectively as defined hereinbefore, m means 2 or 3, and E means an C1 ⁇ 10 alkyl group, an alkylene group, a hydroxyalkyl group, a sulfur-containing alkyl group, an aminoalkyl group or a sulfur-containing aminoalkyl group or the absence of such a group.
  • said quaternary ammonium compound (2) is reacted with a compound of general formula (8) E(COOD) m (8) wherein E and m are respectively as defined above and D means an alkali metal atom or an alkaline earth metal atom in a solvent, such as those mentioned hereinbe­fore, either in the presence of a small amount of the novel oxyalkylated quaternary ammonium compound of general formula (7) or in the absence thereof.
  • Examples of the compound of general formula (8) include potassium maleate, potassium succinate, potas­sium fumarate, sodium malonate, potassium adipate, potassium malate, potassium citrate, sodium tricarballyl­ate, potassium tartarate, potassium aspartate, potassium thiodipropionate, cystine potassium salt, sodium thiodiglycolate, potassium oxalate, potassium aconitate and so on.
  • the reaction ratio of compound (2) to compound (8) may be one mole of compound (2) per carboxyl group of compound (8).
  • the ratio may be 1 to 1.2 carboxyl groups of (8) per mole of compound (2).
  • a still another preferred class of the novel oxyalkylated quaternary ammonium compound according to the present invention can be expressed by the following general formula wherein R1, R2, R3 and R4 are respectively as defined hereinbefore, R7 means a hydrogen atom or an C1 ⁇ 6 alkyl group, and R8 means an C1 ⁇ 6 alkylene group or an aromatic group.
  • This class of compound can be produced by reacting a quaternary ammonium compound of general formula (2) with a compound of general formula (10) R7NHR8SO3D (10) wherein R7, R8 and D are respectively as defined hereinbefore in a solvent, such as those mentioned hereinbefore, either in the presence of a small amount of the novel oxyalkylated quaternary ammonium compound (9) or in the absence thereof.
  • Examples of the compound of general formula (10) include salts of aminoalkylsulfonic acids or aromatic aminosulfonic acids, such as methyltaurine sodium salt, taurine potassium salt, sodium sulfanilate, potassium naphthionate, sodium aminobutanesulfonate, potassium aminomethanesulfonate and so on.
  • the preferred reaction ratio of compound (10) to compound (2) is 1 to 1.5 moles of (10) to each mole of (2).
  • a still another preferred class of the novel oxyalkylated quaternary ammonium compound according to the present invention can be represented by the follow­ing general formula wherein R1, R2, R3 and R4 are respectively as defined hereinbefore and R9 means a hydrogen atom, a saturated or unsaturated C1 ⁇ 22 alkyl group, a hydroxyalkyl group, an alkylene group, a mercaptoalkyl group, an aromatic group, an aromatic group-substituted alkyl group, a hydroxy-containing aromatic group, an alkyl­aryl group,
  • the above compound can be produced by reacting a quaternary ammonium compound of general formula (2) with a compound of general formula (12) R9COOD (12) wherein R9 and D are respectively as defined herein­before in a solvent, such as those mentioned herein­before, either in the presence of a small amount of the novel oxyalkylated quaternary ammonium compound of general formula (11) or in the absence thereof.
  • Examples of compound (12) include, among others, potassium acetate, potassium propionate, sodium glycol­ate, potassium cinnamate, potassium salicylate, sodium acetoacetate, potassium mercaptopropionate, sodium octylate, potassium formate, calcium acrylate, potas­sium gluconate, sodium benzoate, potassium oleate, sodium octylate, potassium pentadecanate, potassium glycolate, potassium crotonate, sodium sorbate, sodium glyoxalate, sodium phenylacetate, potassium ricino­leate, sodium glyoxalate, potassium coumarinate, potassium gallate, potassium lactate, sodium pyruvate, potassium thioglycolate, potassium 1-hydroxy-2,6-di-t-­butylphenyl-4-propionate, potassium toluylate, and so on.
  • the preferred reaction ratio of compound (12) to compound (2) is 1 to 1.5 moles of (12) to each mole of compound (2).
  • a still another preferred class of the novel oxyalkylated quaternary ammonium compound according to the present invention can be represented by the follow­ing general formula wherein R1, R2, R3 and R4 are respectively as defined hereinbefore, n means 1 or 2, and R10 means a straight-chain or branched C1 ⁇ 22 alkyl group, an C1 ⁇ 22 alkyl-containing alkoxypolyethoxyethyl group, an C1 ⁇ 22 alkyl-containing alkylphenoxypolyethoxyethyl group, or a mono-, di- or tristyrylphenoxypolyethoxy­ethyl group, and when there are two R 10's , they may be the same or different.
  • the compound of this class can be produced by reacting a quaternary ammonium compound of general formula (2) with a compound of general formula (14) (R10O) 3-n (OD) n (14) wherein R10, D and n are respectively as defined hereinbefore in a solvent, such as those mentioned hereinbefore, either in the presence of a small amount of the novel oxyalkylated quaternary ammonium compound of general formula (13) or in the absence thereof.
  • Examples of compound (14) include potassium or sodium salts of isopropyl phosphate, diisopropyl phosphate, mono-/di-isooctyl phosphate (mole ratio 1:1), dilauryl phosphate, phenoxyethyl phosphate, diphenoxyethyl phosphate, nonylphenoxytetraethoxyethyl phosphate, mono-/di-lauryloxydiethoxyethyl phosphate (mole ratio 1:1), styrylphenoxyethoxyethyl phosphate, di(distyrylphenoxy)pentaethoxyethyl phosphate and so on.
  • the preferred reaction ratio of compound (2) to compound (14) is 1 to 1.5 moles of (2) to each mole of (14) when n in general formula (14) means 1, and 2 to 3 moles of (2) to each mole of (14) when n means 2. It should be understood that a mixture of compound (14) wherein n is 1 and compound (14) wherein n is 2 can be used for this reaction.
  • the novel oxyalkylated quaternary ammonium compound consisting of a cationic group of general formula (1) and an anionic group selected from the class consisting of carboxylic acid residues, aminosulfonic acid residues and phosphoric acid ester residues can be easily obtained in high yield.
  • the novel oxyalkylated quaternary ammonium compound accord­ing to the present invention is least phytotoxic, exhibits a potent growth modulating action on a broad spectrum of plants and is resistant to the attack of microorganisms. Therefore, the plant growth modulating composition of the present invention is very useful.
  • the oxyalkyl­ated ammonium compound of the invention can be used in the per se known ways.
  • the seeds of plant whose growth is to be regulated may be immersed in an aqueous solution of the compound before sowing.
  • the concentration may range from 0.0001 to 0.1% , for instance, and the immersion time may range from several hours to tens of hours.
  • a four-necked flask fitted with stirrer and condenser means was charged with 37.8 g of lauryl­methyldihydroxyethylammonium bromide, 13.9 g of valine sodium salt, 3 g of laurylmethyldihydroxyethylammonium salt of valine and 200 g of isopropyl alcohol and the reaction was conducted at 50°C in an atmosphere of nitrogen gas introduced at a low flow rate for 4 hours. The precipitate was then collected by filtration and washed with 30 ml of isopropyl alcohol. The filtrate and washings were combined and the isopropyl alcohol was distilled off under reduced pressure.
  • Example 1 The compound synthesized in Example 1 was dis­solved in water to prepare 0.0001%, 0.001%, 0.01% and 0.1% aqueous solutions and soybean, corn and paddy rice seeds were immersed in the solutions at 25°C for 12 hours. Then, polyethylene cups were filled with vermiculite and the above seeds were sown. The cups were placed in a green house maintained at an interior temperature of 25°C and kept for 10 days, with daily replenishment of water. As controls, the corresponding seeds soaked in water were similarly grown.
  • Tables 1 to 3 show the mean stem length and leaves number and mean root length of each plant. It is apparent from the data that the compound according to Example 1 has plant growth regulating activity.
  • Table 1 Effects on the stem length and leaves number and root length of the soybean plant Control Compound of the invention (Example 1) Untreated 0.0001% 0.001% 0.01% 0.1% Stem length, cm 18 18.5 19.3 21.0 19.1 Number of leaves 7.5 7.8 8.3 8.7 7.9 Root length, cm 11 11.3 11.2 12.5 11.5
  • Table 2 Effects on the stem length and leaves number and root length of the corn plant Control Compound of the invention (Example 1) Untreated 0.0001% 0.001% 0.01% 0.1% Stem length, cm 12 16.2 15.8 15.0 15.0 Number of leaves 2.6 3.0 3.2 3 2.8 Root length, cm 16.8 18.4 17.6 23.2 17.8 Table 3 Effects on the stem length and leaves number and root length of the rice plant Control Compound of the invention (Example 1) Untreated 0.0001% 0.001% 0.01% 0.1% Stem length
  • a four-necked flask fitted with stirrer and condenser means was charged with 81 g of oleylmethyldi­hydroxyethylammonium chloride, 20 g of potassium succinate and 200 g of isobutyl alcohol and the reac­tion was conducted at 40-50°C in an atmosphere of nitrogen gas introduced at a low flow rate for 6 hours.
  • the precipitate was then collected by filtration and washed with 30 ml of isobutyl alcohol, and the filtrate and washings were combined and concentrated under reduced pressure.
  • a four-necked flask fitted with stirrer and condenser means was charged with 81 g of oleylmethyl­dihydroxyethylammonium chloride, 33 g of cystine potassium salt and 200 g of isopropyl alcohol and the reaction was conducted at 65-75°C in an atmosphere of nitrogen gas introduced at a low flow rate for 7 hours.
  • the precipitate was then filtered off and the filtrate was concentrated under reduced pressure. The residue was dissolved in 200 g of toluene and the insolubles were filtered off.
  • Example 5 The compound synthesized in Example 5 was dis­solved in water to prepare 0.0001%, 0.001%, 0.01% and 0.1% aqueous solutions and soybean, corn and paddy rice seeds were immersed in the solutions at 25°C for 12 hours. Then, polyethylene cups were filled with vermiculite and the above seeds were sown. The cups were placed in a green house maintained at an interior temperature of 25°C and kept for 10 days, with daily replenishment of water. As controls, the corresponding seeds soaked in water were similarly grown.
  • Tables 4 to 6 show the mean stem length and leaves number and mean root length of each plant. It is apparent from the data that the compound according to Example 5 has plant growth regulating activity for dicotyledons and monocotyledons.
  • Table 4 Effects on the stem length and leaves number and root length of the soybean plant Control Compound of the invention (Example 5) Untreated 0.0001% 0.001% 0.01% 0.1% Stem length, cm 18 25.0 23.0 23.0 18.5 Number of leaves 7.5 10.3 9.2 8.3 7.9 Root length, cm 11.0 14.2 13.5 12.6 11.5
  • Table 5 Effects on the stem length and leaves number and root length of the corn plant Control Compound of the invention (Example 5) Untreated 0.0001% 0.001% 0.01% 0.1% Stem length, cm 12 12.1 16.6 15.6 13.6 Number of leaves 2.6 3 3 3 2.8 Root length, cm 16.8 17.0 23.4 21.4 17.4 Table 6 Effects on the stem length and leaves number and root length of the rice plant Control Compound of the invention (Example
  • Example 10 The compound synthesized in Example 10 is dis­solved in water to prepare 0.0001%, 0.001%, 0.01% and 0.1% aqueous solutions and soybean, corn and paddy rice seeds are immersed in the solutions at 25°C for 12 hours. Then, polyethylene cups are filled with vermiculite and the above seeds are sown. The cups are placed in a green house maintained at an interior temperature of 25°C and kept for 10 days. As controls, the corresponding seeds soaked in water are similarly grown.
  • Tables 7 to 9 show the predicted mean stem length and leaves number and mean root length of each test plant.
  • Example 10 has plant growth regulating activity.
  • Table 7 Effects on the stem length and leaves number and root length of the soybean plant Control Compound of the invention (Example 10) Untreated 0.0001% 0.001% 0.01% 0.1% Stem length, cm 18 22.6 23.0 20.4 19.0 Number of leaves 7.5 8.0 8.9 8.7 8.5 Root length, cm 11.0 13.1 14.2 16.6 11.2
  • Table 8 Effects on the stem length and leaves number and root length of the corn plant Control Compound of the invention (Example 10) Untreated 0.0001% 0.001% 0.01% 0.1% Stem length, cm 12 22.1 24.8 23.6 22.2 Number of leaves 2.6 3.3 3.6 3.0 2.8 Root length, cm 16.8 21.2 22.3 19.2 17.7
  • Table 9 Effects on the stem length and leaves number and root length of the rice plant Control Compound of the invention (Example 10) Untreated 0.0001% 0.001% 0.01% 0.1% Stem length, cm 7.4 8.9 10.1 9.5 8.3 Number of leaves 1.6 2.0 2.4 2.5 2.0 Root length
  • a four-necked flask fitted with stirrer and condenser means was charged with 40.5 g of oleylmethyl­dihydroxyethylammonium chloride, 10 g of potassium formate and 150 g of isopropyl alcohol and the reaction was conducted at 75-80°C in an atmosphere of nitrogen gas introduced at a low flow rate for 8 hours.
  • the precipitate was then collected by filtration and washed with 50 ml of isopropyl alcohol.
  • the filtrate and the washings were combined and concentrated under reduced pressure and the residue was dissolved in 200 g of benzene and filtered.
  • Example 15 The compound synthesized in Example 15 is dis­solved in water to prepare 0.0001%, 0.001%, 0.01% and 0.1% aqueous solutions and soybean, corn and paddy rice seeds are immersed in the solutions at 25°C for 12 hours. Then, polyethylene cups are filled with vermi­culite and the above seeds are sown. The cups are placed in a green house maintained at an interior temperature of 25°C and kept for 10 days, with daily replenishment of water. As controls, the corresponding seeds soaked in water are similarly grown.
  • Tables 10 to 12 show the predicted mean stem length and leaves number, mean root length, and germi­nation rate of each plant.
  • the compound of Example 15 is expected to inhibit the germination of soybean seeds at all concentrations.
  • the compound is expected to inhibit germination over the concentration range of 0.001 to 0.1% as will be seen from Table 11.
  • the compound is expected to suppress growth at all concentrations.
  • Example 18 The compound synthesized in Example 18 is dis­solved in water to prepare 0.0001%, 0.001%, 0.01% and 0.1% aqueous solutions and soybean, corn and paddy rice seeds are immersed in the solutions at 25°C for 12 hours. Then, polyethylene cups are filled with vermi­culite and the above seeds are sown. The cups are placed in a green house maintained at an interior temperature of 25°C and kept for 10 days, with daily replenishment of water. As controls, the corresponding seeds soaked in water are similarly grown.
  • Tables 13 to 15 show the predicted mean stem length and leaves number and mean root length of each plant.
  • Example 18 has plant growth regulating activity.
  • Table 13 Effects on the stem length and leaves number and root length of the soybean plant Control Compound of the invention (Example 18) Untreated 0.0001% 0.001% 0.01% 0.1% Stem length, cm 18 22.7 23.9 23.0 22.7 Number of leaves 7.5 8.3 9.3 11.3 7.9 Root length, cm 11.0 12.0 12.1 11.6 11.1
  • Table 14 Effects on the stem length and leaves number and root length of the corn plant Control Compound of the invention (Example 18) Untreated 0.0001% 0.001% 0.01% 0.1% Stem length, cm 12 15.9 16.9 17.6 15.6 Number of leaves 2.6 2.9 3.1 2.6 3.1 Root length, cm 16.8 18.0 21.0 20.6 19.5
  • Table 15 Effects on the stem length and leaves number and root length of the rice plant Control Compound of the invention (Example 18) Untreated 0.0001% 0.001% 0.01% 0.1% Stem length, cm 7.4 9.5 10.2 8.9 10.2 Number of leaves 1.6 2.4 2.6 2.2

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Abstract

This invention relates to novel oxyalkylated quaternary ammonium compounds, processes for their production and plant growth regulating compositions containing the same compounds. Each of these oxyalkyl­ated quaternary ammonium compounds consists of an oxyalkylated quaternary ammonium cation and an anion selected from among carboxylic acid residues, amino­sulfonic acid residues and phosphoric acid ester residues. These oxyalkylated quaternary ammonium compounds are least phytotoxic, produce marked growth regulating effects on a broad species of plants and are not easily decomposed by microorganisms.

Description

    BACKGROUND OF THE INVENTION
  • The present invention relates to novel oxyalkyl­ated quaternary ammonium compounds, processes for production thereof and plant growth regulating composi­tions containing said compounds.
  • A large number of chemicals are known to regulate or modulate growth of plants but most of such agro­chemicals heretofore available are either injurious to crop plants or effective for only limited varieties of plants.
  • Furthermore, even if they do little harm to plants, many chemicals are so readily decomposed by microorganisms that they cannot exhibit a sufficient regulating effect on plant growth under field condi­tions (Japanese Kokai Patent Publication No. 61-24501, No. 61-91104, No. 61-91105, No. 61-91106, No. 62-26205, and No. 62-294603).
    • SUMMARY OF THE INVENTION
  • It is an object of the present invention to provide a novel oxyalkylated quaternary ammonium compound which is least phytotoxic, exerts a potent plant growth regulating action on a broad species of plants and is not easily decomposed by microorganisms.
  • It is another object to provide processes for production of said compound.
  • It is a still another object to provide a plant growth regulating composition containing said compound as an active ingredient.
  • The novel oxyalkylated quaternary ammonium com­pound of the present invention consists of a cationic group of the general formula
    Figure imgb0001
     wherein R₁ means an C₆₋₂₂ alkyl or alkenyl group, R₂ means an C₁₋₄ alkyl or hydroxyalkyl group and R₃ and R₄ independently mean (BO)xH where B is an C₁₋₄ alkylene group and x means a whole or fractional number of 1 to 5 and an anionic group selected from the class consisting of carboxylic acid residues, amino­sulfonic acid residues and phosphate ester residues.
  • The processes for producing said oxyalkylated quaternary ammonium compound in accordance with the invention generally comprise reacting a quaternary ammonium compound of the general formula
    Figure imgb0002
     wherein R₁, R₂, R₃ and R₄ are respectively as defined above and Y means Cl, Br, I or F with at least one member of the class consisting of alkali metal salts of carboxylic acids, alkaline earth metal salts of carboxylic acids, alkali metal salts of aminosulfonic acids, alkaline earth metal salts of aminosulfonic acids, alkali metal salts of phosphoric acid esters and alkaline earth metal salts of phosphoric acid esters in a solvent, either in the presence of a small amount of said novel oxyalkylated quaternary ammonium compound or in the absence thereof. The solvent mentioned just above is preferably selected from the class consisting of straight-chain or branched C₁₋₆ alcohols, methyl ethyl ketone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, dioxane, ethyl acetate and cyclo­hexanol, and these solvents may be used singly or in combination.
  • The plant growth regulating composition of the present invention contains the above-mentioned novel oxyalkylated quaternary ammonium compound.
    • DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
  • The reaction for production of the novel oxyalkyl­ated quaternary ammonium compound is generally con­ducted at 30 to 100°C for about 3 to 24 hours.
  • After completion of the reaction, the byproduced alkali metal halide or alkaline earth metal halide is filtered off and the solvent is removed from the filtrate to isolate the object compound.
  • If the produced compound is to be further pu­rified, the residue on evaporation of the solvent is dissolved in a solvent, such as a straight-chain or branched C₁₋₆ alcohol, acetone, methyl ethyl ketone, n-hexane, cyclohexane, benzene, toluene, xylene or the like or an appropriate mixture of such solvents and the solution is filtered. The filtrate is then concen­trated or cooled to recover purified materials.
  • Preferred examples of the solvent to be used in the production processes of the present invention include, as aforesaid, straight-chain or branched C₁₋₆ alcohols, ethyl acetate, dioxane, methyl ethyl ketone, cyclohexanol, dimethyl sulfoxide, dimethylform­amide and dimethylacetamide, although other solvents may likewise be employed unless they interfere with the intended reaction. The preferred amount of the solvent is one to 10-fold by weight relative to the combined weight of said compound (2) and said alkali metal salt or alkaline earth metal salt.
  • It should be understood that the presence of water in the reaction system in a proportion not exceeding about 10 weight percent of the above-mentioned combined weight does not interfere with the reaction.
  • The reaction can also be conducted in the presence of not more than about 10 weight percent of the novel oxyalkylated quaternary ammonium compound of the invention relative to the above-mentioned combined weight. In such a case or when the compound (2) is the chloride or bromide, an alkali iodide may be added in a proportion of not more than 10 weight percent of com­pound (2). Furthermore, in order to prevent discolora­tion of the reaction system, nitrogen gas may be intro­duced into the reaction system at a low flow rate.
  • A preferred class of the novel oxyalkylated quaternary ammonium compound according to the present invention can be written as follows.
    Figure imgb0003
     wherein R₁, R₂, R₃ and R₄ are respectively as defined hereinbefore, A⊖ is R₅NHR₆COO⊖,
    Figure imgb0004
     where R₅ means a hydrogen atom, an C₁₋₄ alkyl group,
    Figure imgb0005
     NH₂CH₂(CH₂)₃-, or HSCH₂-, and R₆ means CH, CH₂ or an aromatic group.
  • The process for producing the above compound (3) comprises reacting a quaternary ammonium compound of general formula (2) with a compound of general formula (4)
    R₅NHR₆COOD      (4),
    a compound of general formula (5)
    Figure imgb0006
     or a compound of general formula (6)
    Figure imgb0007
     wherein R₅ and R₆ are as defined hereinbefore and D means an alkali metal atom or an alkaline earth metal atom in a solvent, such as those mentioned hereinbe­fore, either in the presence of a small amount of the novel oxyalkylated quaternary ammonium compound (3) or in the absence thereof.
  • Examples of compound (2) include, among others, octylmethyldihydroxyethylammonium chloride, lauryl­methyldihydroxyethylammonium bromide, oleylethyldi­hydroxyethylammonium iodide, stearylmethyldihydroxypro­pylammonium chloride, hexylethyldihydroxybutylammonium bromide, oleyltrihydroxyethylammonium chloride, lauryl­ trihydroxyethylammonium chloride, stearyltrihydroxy­ethylammonium chloride, oleyltrihydroxyethylammonium bromide, octyldihydroxyethylhydroxypropylammonium chloride, oleylmethyldihydroxyethoxyethylammonium chloride and so on.
  • Examples of the compound of general formula (4), (5), or (6) include alkali metal or alkaline earth metal salts of amino acids such as glycine potassium salt, sarcosine sodium salt, alanine potassium salt, leucine potassium salt, valine sodium salt, cysteine sodium salt, potasssium indoleacetate, potassium pyrrolidonecarboxylate, serine calcium salt, methionine potassium salt, proline potassium salt, tryptophan sodium salt, lysine calcium salt, potassium aminobenzo­ate and so on.
  • The preferred ratio of compound (4), (5) or (6) to compound (2) is 1 to 1.5 moles of (4), (5) or (6) to each mole of (2).
  • An example of the reaction may be written as follows.
    Figure imgb0008
  • Another preferred class of the novel oxyalkylated quaternary ammonium compound according to the present inevention can be expressed by the general formula
    Figure imgb0009
     wherein R₁, R₂, R₃ and R₄ are respectively as defined hereinbefore, m means 2 or 3, and E means an C₁₋₁₀ alkyl group, an alkylene group, a hydroxyalkyl group, a sulfur-containing alkyl group, an aminoalkyl group or a sulfur-containing aminoalkyl group or the absence of such a group.
  • For the production of the above compound (7), said quaternary ammonium compound (2) is reacted with a compound of general formula (8)
    E(COOD)m      (8)
    wherein E and m are respectively as defined above and D means an alkali metal atom or an alkaline earth metal atom in a solvent, such as those mentioned hereinbe­fore, either in the presence of a small amount of the novel oxyalkylated quaternary ammonium compound of general formula (7) or in the absence thereof.
  • As compound (2) for this reaction, any of the specific compounds (2) mentioned hereinbefore, for instance, can be employed.
  • Examples of the compound of general formula (8) include potassium maleate, potassium succinate, potas­sium fumarate, sodium malonate, potassium adipate, potassium malate, potassium citrate, sodium tricarballyl­ate, potassium tartarate, potassium aspartate, potassium thiodipropionate, cystine potassium salt, sodium thiodiglycolate, potassium oxalate, potassium aconitate and so on.
  • The reaction ratio of compound (2) to compound (8) may be one mole of compound (2) per carboxyl group of compound (8). The ratio may be 1 to 1.2 carboxyl groups of (8) per mole of compound (2).
  • This reaction can be written as follows.
    Figure imgb0010
  • A still another preferred class of the novel oxyalkylated quaternary ammonium compound according to the present invention can be expressed by the following general formula
    Figure imgb0011
     wherein R₁, R₂, R₃ and R₄ are respectively as defined hereinbefore, R₇ means a hydrogen atom or an C₁₋₆ alkyl group, and R₈ means an C₁₋₆ alkylene group or an aromatic group.
  • This class of compound can be produced by reacting a quaternary ammonium compound of general formula (2) with a compound of general formula (10)
    R₇NHR₈SO₃D      (10)
    wherein R₇, R₈ and D are respectively as defined hereinbefore in a solvent, such as those mentioned hereinbefore, either in the presence of a small amount of the novel oxyalkylated quaternary ammonium compound (9) or in the absence thereof.
  • As compound (2) for this reaction, any of the specific compounds (2) mentioned hereinbefore, for instance can be employed.
  • Examples of the compound of general formula (10) include salts of aminoalkylsulfonic acids or aromatic aminosulfonic acids, such as methyltaurine sodium salt, taurine potassium salt, sodium sulfanilate, potassium naphthionate, sodium aminobutanesulfonate, potassium aminomethanesulfonate and so on.
  • The preferred reaction ratio of compound (10) to compound (2) is 1 to 1.5 moles of (10) to each mole of (2).
  • This reaction may be written as follows.
    Figure imgb0012
  • A still another preferred class of the novel oxyalkylated quaternary ammonium compound according to the present invention can be represented by the follow­ing general formula
    Figure imgb0013
     wherein R₁, R₂, R₃ and R₄ are respectively as defined hereinbefore and R₉ means a hydrogen atom, a saturated or unsaturated C₁₋₂₂ alkyl group, a hydroxyalkyl group, an alkylene group, a mercaptoalkyl group, an aromatic group, an aromatic group-substituted alkyl group, a hydroxy-containing aromatic group, an alkyl­aryl group,
    Figure imgb0014
  • The above compound can be produced by reacting a quaternary ammonium compound of general formula (2) with a compound of general formula (12)
    R₉COOD      (12)
    wherein R₉ and D are respectively as defined herein­before in a solvent, such as those mentioned herein­before, either in the presence of a small amount of the novel oxyalkylated quaternary ammonium compound of general formula (11) or in the absence thereof.
  • As compound (2) for this reaction, any of the various specific compounds (2) mentioned hereinbefore, for instance, can be employed.
  • Examples of compound (12) include, among others, potassium acetate, potassium propionate, sodium glycol­ate, potassium cinnamate, potassium salicylate, sodium acetoacetate, potassium mercaptopropionate, sodium octylate, potassium formate, calcium acrylate, potas­sium gluconate, sodium benzoate, potassium oleate, sodium octylate, potassium pentadecanate, potassium glycolate, potassium crotonate, sodium sorbate, sodium glyoxalate, sodium phenylacetate, potassium ricino­leate, sodium glyoxalate, potassium coumarinate, potassium gallate, potassium lactate, sodium pyruvate, potassium thioglycolate, potassium 1-hydroxy-2,6-di-t-­butylphenyl-4-propionate, potassium toluylate, and so on.
  • The preferred reaction ratio of compound (12) to compound (2) is 1 to 1.5 moles of (12) to each mole of compound (2).
  • A still another preferred class of the novel oxyalkylated quaternary ammonium compound according to the present invention can be represented by the follow­ing general formula
    Figure imgb0015
     wherein R₁, R₂, R₃ and R₄ are respectively as defined hereinbefore, n means 1 or 2, and R₁₀ means a straight-chain or branched C₁₋₂₂ alkyl group, an C₁₋₂₂ alkyl-containing alkoxypolyethoxyethyl group, an C₁₋₂₂ alkyl-containing alkylphenoxypolyethoxyethyl group, or a mono-, di- or tristyrylphenoxypolyethoxy­ethyl group, and when there are two R10's, they may be the same or different.
  • The compound of this class can be produced by reacting a quaternary ammonium compound of general formula (2) with a compound of general formula (14)

    (R₁₀O)3-n
    Figure imgb0016
    (OD)n      (14)
    wherein R₁₀, D and n are respectively as defined hereinbefore in a solvent, such as those mentioned hereinbefore, either in the presence of a small amount of the novel oxyalkylated quaternary ammonium compound of general formula (13) or in the absence thereof.
  • As compound (2) for this reaction, any of the various compounds (2) mentioned hereinbefore, for instance, can be employed.
  • Examples of compound (14) include potassium or sodium salts of isopropyl phosphate, diisopropyl phosphate, mono-/di-isooctyl phosphate (mole ratio 1:1), dilauryl phosphate, phenoxyethyl phosphate, diphenoxyethyl phosphate, nonylphenoxytetraethoxyethyl phosphate, mono-/di-lauryloxydiethoxyethyl phosphate (mole ratio 1:1), styrylphenoxyethoxyethyl phosphate, di(distyrylphenoxy)pentaethoxyethyl phosphate and so on.
  • The preferred reaction ratio of compound (2) to compound (14) is 1 to 1.5 moles of (2) to each mole of (14) when n in general formula (14) means 1, and 2 to 3 moles of (2) to each mole of (14) when n means 2. It should be understood that a mixture of compound (14) wherein n is 1 and compound (14) wherein n is 2 can be used for this reaction.
  • In accordance with the production processes of the present invention, the novel oxyalkylated quaternary ammonium compound consisting of a cationic group of general formula (1) and an anionic group selected from the class consisting of carboxylic acid residues, aminosulfonic acid residues and phosphoric acid ester residues can be easily obtained in high yield. The novel oxyalkylated quaternary ammonium compound accord­ing to the present invention is least phytotoxic, exhibits a potent growth modulating action on a broad spectrum of plants and is resistant to the attack of microorganisms. Therefore, the plant growth modulating composition of the present invention is very useful.
  • For use as a plant growth modulator, the oxyalkyl­ated ammonium compound of the invention can be used in the per se known ways. For example, the seeds of plant whose growth is to be regulated may be immersed in an aqueous solution of the compound before sowing. Although the optimum concentration of the solution and the immersion time vary with different plants, the concentration may range from 0.0001 to 0.1% , for instance, and the immersion time may range from several hours to tens of hours.
  • The following examples are merely intended to illustrate the invention in further detail and should by no means be construed as defining the scope of the invention.
    • Example 1
  • A four-necked flask fitted with stirrer and condenser means was charged with 40.5 g of oleylmethyl­dihydroxyethylammonium chloride, 13 g of potassium glycinate and 200 g of isobutyl alcohol and the reaction was conducted at 40-50°C in an atmosphere of nitrogen gas introduced at a low flow rate for 6 hours. The precipitate was then collected by filtration and washed with 30 ml of isobutyl alcohol. The filtrate and the washings were combined and concentrated under reduced pressure. The residue was dissolved in 200 g of toluene and filtered. The filtrate was then concen­trated to give 43.1 g (theoretical yield 44.4 g) of oleylmethyldihydroxyethylammonium glycinate as a waxy product. The elemental analysis and infrared absorp­tion data are given below.
    Analysis (%; calcd. in parentheses)
    C, 67.05 (67.56)
    H, 11.75 (11.71)
    O, 14.18 (14.41)
    N, 6.21 ( 6.30)
    Cl, 0.01
    IR
  • In addition to the absorptions of oleylmethyldi­ hydroxyethylammonium, absorptions assignable to -COO⊖ of glycine were observed at 1600 cm⁻¹ and 1380 cm⁻¹.
    • Example 2
  • A four-necked flask fitted with stirrer and condenser means was charged with 37.8 g of lauryl­methyldihydroxyethylammonium bromide, 13.9 g of valine sodium salt, 3 g of laurylmethyldihydroxyethylammonium salt of valine and 200 g of isopropyl alcohol and the reaction was conducted at 50°C in an atmosphere of nitrogen gas introduced at a low flow rate for 4 hours. The precipitate was then collected by filtration and washed with 30 ml of isopropyl alcohol. The filtrate and washings were combined and the isopropyl alcohol was distilled off under reduced pressure. The residue was then dissolved in 200 g of benzene and the in­solubles were filtered off. Finally, the benzene was distilled off to give 39.3 g (theoretical yield 41.4 g) of laurylmethyldihydroxyethylammonium salt of valine as a waxy product.
    Analysis (%; calcd. in parentheses)
    C, 63.58 (63.76)
    H, 11.53 (11.59)
    O, 15.40 (15.45)
    N, 6.71 ( 6.76)
    Br, 0.02
    • Example 3
  • A four-necked flask fitted with stirrer and condenser means was charged with 32.5 g of decyltri­hydroxyethylammonium chloride, 200 g of isopropyl alcohol, 25.6 g of tryptophan potassium salt and 3 g of potassium iodide and the reaction was conducted at 60°C for 8 hours. The reaction mixture was then allowed to stand overnight and the precipitate was collected by filtration and washed with 200 g of isopropyl alcohol. The filtrate and the washings were combined and con­centrated. The residue was dissolved in 200 g of toluene and the insolubles were filtered off. Finally, the filtrate was concentrated to give 45.6 g (theore­tical yield 48.1 g) of decyltrihydroxyethylammonium salt of tryptophan as a waxy product.
    Analysis (%; cald. in parentheses)
    C, 63.98 (64.86)
    H, 9.79 ( 9.77)
    N, 8.68 ( 8.73)
    O, 16.51 (16.63)
    Cl, 0.02
    • Example 4
  • The compound synthesized in Example 1 was dis­solved in water to prepare 0.0001%, 0.001%, 0.01% and 0.1% aqueous solutions and soybean, corn and paddy rice seeds were immersed in the solutions at 25°C for 12 hours. Then, polyethylene cups were filled with vermiculite and the above seeds were sown. The cups were placed in a green house maintained at an interior temperature of 25°C and kept for 10 days, with daily replenishment of water. As controls, the corresponding seeds soaked in water were similarly grown.
  • Tables 1 to 3 show the mean stem length and leaves number and mean root length of each plant. It is apparent from the data that the compound according to Example 1 has plant growth regulating activity. Table 1
    Effects on the stem length and leaves number and root length of the soybean plant
    Control Compound of the invention (Example 1)
    Untreated 0.0001% 0.001% 0.01% 0.1%
    Stem length, cm 18 18.5 19.3 21.0 19.1
    Number of leaves 7.5 7.8 8.3 8.7 7.9
    Root length, cm 11 11.3 11.2 12.5 11.5
    Table 2
    Effects on the stem length and leaves number and root length of the corn plant
    Control Compound of the invention (Example 1)
    Untreated 0.0001% 0.001% 0.01% 0.1%
    Stem length, cm 12 16.2 15.8 15.0 15.0
    Number of leaves 2.6 3.0 3.2 3 2.8
    Root length, cm 16.8 18.4 17.6 23.2 17.8
    Table 3
    Effects on the stem length and leaves number and root length of the rice plant
    Control Compound of the invention (Example 1)
    Untreated 0.0001% 0.001% 0.01% 0.1%
    Stem length, cm 7.4 11.8 13.0 12.2 9.6
    Number of leaves 1.6 2 2 2 2
    Root length, cm 11.0 12.8 14.2 12.6 11.6
    • Example 5
  • A four-necked flask fitted with stirrer and condenser means was charged with 81 g of oleylmethyldi­hydroxyethylammonium chloride, 20 g of potassium succinate and 200 g of isobutyl alcohol and the reac­tion was conducted at 40-50°C in an atmosphere of nitrogen gas introduced at a low flow rate for 6 hours. The precipitate was then collected by filtration and washed with 30 ml of isobutyl alcohol, and the filtrate and washings were combined and concentrated under reduced pressure. The residue was dissolved in 200 g of toluene and filtered and the filtrate was concen­trated to give 82 g (theoretical yield 85.6 g) of di(oleylmethyldihydroxyethylammonium) succinate as a waxy product. The elemental analysis and IR data are shown below.
    Analysis (%; calcd. in parentheses)
    C, 70.65 (70.09)
    H, 11.61 (11.68)
    O, 14.89 (14.95)
    N, 3.32 ( 3.27)
    Cl, 0.01
    IR
  • In addition to the absorptions of oleylmethyldi­hydroxyethylammonium, absorptions assignable to -COO⊖ of the succinate were found at 1570 cm⁻¹ and 1380 cm⁻¹.
    • Example 6
  • A four-necked flask fitted with stirrer and condenser means was charged with 73.6 g of lauryl­methyldihydroxyethylammonium bromide, 19.0 g of sodium aspartate, 200 g of isopropyl alcohol and 3.5 g of di(laurylmethyldihydroxyethylammonium) aspartate and the reaction was conducted at 50°C in an atmosphere of nitrogen gas introduced at a low flow rate for 4 hours. The precipitate was then collected by filtration and washed with 30 ml of isopropyl alcohol. The filtrate and washings were combined and the isopropyl alcohol was distilled off under reduced pressure. The residue was dissolved in toluene and the insolubles were filtered off. Finally, the toluene was distilled off under reduced pressure to give 65.7 g (theoretical yield 70.7 g) of di(laurylmethyldihydroxyethylammonium) aspartate as a waxy product.
    Analysis (%; calcd. in parentheses)
    C, 64.53 (64.49)
    H, 11.40 (11.45)
    O, 17.98 (18.10)
    N, 5.91 ( 5.94)
    Br, 0.008
    • Example 7
  • A four-necked flask fitted with stirrer and condenser means was charged with 81 g of oleylmethyl­dihydroxyethylammonium chloride, 33 g of cystine potassium salt and 200 g of isopropyl alcohol and the reaction was conducted at 65-75°C in an atmosphere of nitrogen gas introduced at a low flow rate for 7 hours. The precipitate was then filtered off and the filtrate was concentrated under reduced pressure. The residue was dissolved in 200 g of toluene and the insolubles were filtered off. Finally, the filtrate was concen­trated to give 95.2 g (theoretical yield 97.8 g) of di(oleylmethyldihydroxyethylammonium) cystinate as a waxy product.
    Analysis (%; calcd. in parentheses)
    C, 63.72 (63.80)
    H, 10.78 (10.83)
    O, 13.01 (13.08)
    N, 5.66 ( 5.72)
    S, 6.52 ( 6.54)
    Cl, 0.008
    • Example 8
  • A four-necked flask fitted with stirrer and condenser means was charged with 87.1 g of oleyltri­hydroxyethylammonium chloride, 21 g of sodium tartarate and 200 g of isobutyl alcohol and the reaction was conducted at 80-90°C for 7 hours. The precipitate was then filtered off and the filtrate was concentrated under reduced pressure. The residue was dissolved in 200 g of acetone and the insolubles were filtered off. Finally, the filtrate was concentrated to give 90 g (theoretical yield 94.8 g) of di(oleyltrihydroxyethyl­ammonium) tartarate as a waxy product.
    Analysis (%; calcd. in parentheses)
    C, 65.79 (65.82)
    H, 10.93 (10.97)
    O, 20.21 (20.25)
    N, 2.89 ( 2.95)
    Cl, 0.1
    • Example 9
  • The compound synthesized in Example 5 was dis­solved in water to prepare 0.0001%, 0.001%, 0.01% and 0.1% aqueous solutions and soybean, corn and paddy rice seeds were immersed in the solutions at 25°C for 12 hours. Then, polyethylene cups were filled with vermiculite and the above seeds were sown. The cups were placed in a green house maintained at an interior temperature of 25°C and kept for 10 days, with daily replenishment of water. As controls, the corresponding seeds soaked in water were similarly grown.
  • Tables 4 to 6 show the mean stem length and leaves number and mean root length of each plant. It is apparent from the data that the compound according to Example 5 has plant growth regulating activity for dicotyledons and monocotyledons. Table 4
    Effects on the stem length and leaves number and root length of the soybean plant
    Control Compound of the invention (Example 5)
    Untreated 0.0001% 0.001% 0.01% 0.1%
    Stem length, cm 18 25.0 23.0 23.0 18.5
    Number of leaves 7.5 10.3 9.2 8.3 7.9
    Root length, cm 11.0 14.2 13.5 12.6 11.5
    Table 5
    Effects on the stem length and leaves number and root length of the corn plant
    Control Compound of the invention (Example 5)
    Untreated 0.0001% 0.001% 0.01% 0.1%
    Stem length, cm 12 12.1 16.6 15.6 13.6
    Number of leaves 2.6 3 3 3 2.8
    Root length, cm 16.8 17.0 23.4 21.4 17.4
    Table 6
    Effects on the stem length and leaves number and root length of the rice plant
    Control Compound of the invention (Example 5)
    Untreated 0.0001% 0.001% 0.01% 0.1%
    Stem length, cm 7.4 12.2 14.6 13.9 12.3
    Number of leaves 1.6 2 2.3 2.0 2
    Root length, cm 11.0 15.4 13.6 13.2 13
    • Example 10
  • A four-necked flask fitted with stirrer and condenser means was charged with 39 g of oleylmethyl­dihydroxyethylammonium chloride, 18 g of methyltaurine sodium salt and 200 g of isobutyl alcohol and the reaction was conducted at 40-50°C in an atmosphere of nitrogen gas introduced at a low flow rate for 6 hours. The precipitate was then collected by filtration and washed with 30 ml of isobutyl alcohol. The filtrate and the washings were combined and concentrated under reduced pressure. The residue was dissolved in 200 g of toluene and filtered. The filtrate was then concen­trated to give 46.3 g (theoretical yield 49.2 g) of oleylmethyldihydroxyethylammonium methyltaurate as a waxy product. The elemental analysis and infrared absorption data are given below.
    Analysis (%; calcd. in parentheses)
    C, 60.53 (60.91)
    H, 11.31 (11.37)
    O, 16.09 (16.24)
    N, 5.58 ( 5.68)
    S, 6.46 ( 6.49)
    Cl, 0.01
    IR
  • In addition to the absorptions of oleylmethyldi­hydroxyethylammonium, absorptions assignable to SO₃ of methyltaurine were observed at 1200 cm⁻¹, 1030 cm⁻¹, 610 cm⁻¹ and 520 cm⁻¹.
    • Example 11
  • A four-necked flask fitted with stirrer and condenser means was charged with 39 g of oleylmethyl­dihydroxyethylammonium chloride, 23 g of potassium sulfanilate and 200 g of isobutyl alcohol and the reaction was conducted at 40-50°C in an atmosphere of nitrogen gas introduced at a low flow rate for 6 hours. The precipitate was then collected by filtration and washed with 30 ml of isobutyl alcohol. The filtrate and the washings were combined and concentrated under reduced pressure. The residue was dissolved in 200 g of toluene and filtered. The filtrate was then concen­trated to give 49.8 g (theoretical yield 54.2 g) of oleylmethyldihydroxyethylammonium sulfanilate as a waxy product. The elemental analysis is shown below.
    Analysis (%; calcd. in parentheses)
    C, 63.90 (64.20)
    H, 9.85 ( 9.96)
    N, 5.10 ( 5.16)
    O, 14.55 (14.76)
    S, 5.89 ( 5.90)
    • Example 12
  • A four-necked flask fitted with stirrer and condenser means was charged with 39.8 g of lauryltri­hydroxyethylammonium bromide, 15.9 g of sodium amino­methanesulfonate and 200 g of isopropyl alcohol and the reaction was conducted at 70-80°C in an atmosphere of nitrogen gas introduced at a low flow rate for 5 hours. The precipitate was then filtered off and the filtrate was concentrated. The residue was dissolved in 200 g of isopropyl alcohol and the insolubles were filtered off. Finally, the filtrate was concentrated to give 40.1 g (theoretical yield 42.8 g) of lauryltrihydroxy­ethylammonium aminomethanesulfonate as a waxy product. The elemental analysis is shown below.
    Analysis (%; calcd. in parentheses)
    C, 55.52 (55.60)
    N, 6.44 ( 6.54)
    H, 10.31 (10.28)
    O, 22.29 (22.43)
    S, 7.51 ( 7.47)
    • Example 13
  • The compound synthesized in Example 10 is dis­solved in water to prepare 0.0001%, 0.001%, 0.01% and 0.1% aqueous solutions and soybean, corn and paddy rice seeds are immersed in the solutions at 25°C for 12 hours. Then, polyethylene cups are filled with vermiculite and the above seeds are sown. The cups are placed in a green house maintained at an interior temperature of 25°C and kept for 10 days. As controls, the corresponding seeds soaked in water are similarly grown.
  • Tables 7 to 9 show the predicted mean stem length and leaves number and mean root length of each test plant.
  • It is apparent that the compound of Example 10 has plant growth regulating activity. Table 7
    Effects on the stem length and leaves number and root length of the soybean plant
    Control Compound of the invention (Example 10)
    Untreated 0.0001% 0.001% 0.01% 0.1%
    Stem length, cm 18 22.6 23.0 20.4 19.0
    Number of leaves 7.5 8.0 8.9 8.7 8.5
    Root length, cm 11.0 13.1 14.2 16.6 11.2
    Table 8
    Effects on the stem length and leaves number and root length of the corn plant
    Control Compound of the invention (Example 10)
    Untreated 0.0001% 0.001% 0.01% 0.1%
    Stem length, cm 12 22.1 24.8 23.6 22.2
    Number of leaves 2.6 3.3 3.6 3.0 2.8
    Root length, cm 16.8 21.2 22.3 19.2 17.7
    Table 9
    Effects on the stem length and leaves number and root length of the rice plant
    Control Compound of the invention (Example 10)
    Untreated 0.0001% 0.001% 0.01% 0.1%
    Stem length, cm 7.4 8.9 10.1 9.5 8.3
    Number of leaves 1.6 2.0 2.4 2.5 2.0
    Root length, cm 11.0 13.5 17.5 15.3 14.8
    • Example 14
  • A four-necked flask fitted with stirrer and condenser means was charged with 40.5 g of oleylmethyl­dihydroxyethylammonium chloride, 12.0 g of potassium glycolate and 200 g of isobutyl alcohol and the reaction was conducted at 80-85°C in an atmosphere of nitrogen gas introduced at a low flow rate for 7 hours. The precipitate was then collected by filtration and washed with 30 ml of isobutyl alcohol. The filtrate and the washings were combined and concentrated under reduced pressure and the residue was dissolved in 200 g of toluene and filtered. The filtrate was then concen­trated to give 41.0 g (theoretical yield 44.3 g) of oleylmethyldihydroxyethylammonium glycolate as a waxy product. The elemental analysis and infrared absorp­tion data are given below.
    Analysis (%; calcd. in parentheses)
    C, 67.10 (67.72)
    H, 10.89 (11.06)
    O, 18.20 (18.06)
    N, 3.03 ( 3.16)
    Cl, 0.1
    IR
  • In addition to the absorptions of oleylmethyldi­hydroxyethylammonium, absorptions assignable to -COO⊖ of glycolic acid were observed at 1580 cm⁻¹ and 1385 cm⁻¹.
    • Example 15
  • A four-necked flask fitted with stirrer and condenser means was charged with 40.5 g of oleylmethyl­dihydroxyethylammonium chloride, 10 g of potassium formate and 150 g of isopropyl alcohol and the reaction was conducted at 75-80°C in an atmosphere of nitrogen gas introduced at a low flow rate for 8 hours. The precipitate was then collected by filtration and washed with 50 ml of isopropyl alcohol. The filtrate and the washings were combined and concentrated under reduced pressure and the residue was dissolved in 200 g of benzene and filtered. Finally, the filtrate was concentrated to give 39.3 g (theoretical yield 41.3 g) of oleylmethyldihydroxyethylammonium formate as a waxy product. The elemental analysis and infrared absorp­tion data are given below.
    Analysis (%; calcd. in parentheses)
    C, 69.21 (69.73)
    H, 11.43 (11.38)
    O, 15.11 (15.49)
    N, 3.29 ( 3.38)
    Cl, 0.05
    IR
  • In addition to the absorptions of oleylmethyldi­hydroxyethylammonium, absorptions assignable to -COO⊖ of formic acid were observed at 1590 cm⁻¹ and 1380 cm⁻¹.
    • Example 16
  • A four-necked flask fitted with stirrer and condenser means was charged with 43.3 g of oleyltri­hydroxyethylammonium chloride, 20 g of sodium cinnamate and 200 g of isobutyl alcohol and the reaction was conducted at 40-50°C in an atmosphere of nitrogen gas introduced at a low flow rate for 6 hours. The pre­ cipitate was then collected by filtration and washed with 30 ml of isobutyl alcohol. The filtrate and the washings were combined and concentrated under reduced pressure and the residue was dissolved in 200 g of toluene and filtered. Finally, the filtrate was concentrated to give 50.9 g (theoretical yield 54.5 g) of oleyltrihydroxyethylammonium cinnamate as a waxy product. The elemental analysis is shown below.
    Analysis (%; calcd. in parentheses)
    C, 72.63 (72.59)
    H, 9.97 (10.08)
    O, 14.51 (14.66)
    N, 2.58 ( 2.56)
    Cl, 0.07
    • Example 17
  • The compound synthesized in Example 15 is dis­solved in water to prepare 0.0001%, 0.001%, 0.01% and 0.1% aqueous solutions and soybean, corn and paddy rice seeds are immersed in the solutions at 25°C for 12 hours. Then, polyethylene cups are filled with vermi­culite and the above seeds are sown. The cups are placed in a green house maintained at an interior temperature of 25°C and kept for 10 days, with daily replenishment of water. As controls, the corresponding seeds soaked in water are similarly grown.
  • Tables 10 to 12 show the predicted mean stem length and leaves number, mean root length, and germi­nation rate of each plant. As inferred from Table 10, the compound of Example 15 is expected to inhibit the germination of soybean seeds at all concentrations. As to the corn, the compound is expected to inhibit germination over the concentration range of 0.001 to 0.1% as will be seen from Table 11. Regarding the rice plant, as shown in Table 12, the compound is expected to suppress growth at all concentrations. Table 10
    Effects on the stem length and leaves number and root length of the soybean plant
    Control Compound of the invention (Example 15)
    Untreated 0.0001% 0.001% 0.01% 0.1%
    Stem length, cm 18 9.6 5.3 5.1 5.0
    Number of leaves 7.5 2.5 5.0 3.3 3.3
    Root length, cm 11.0 3.5 3.3 8.0 6.0
    Germination rate, % 100 30 30 10 10
    Table 11
    Effects on the stem length and leaves number and root length of the corn plant
    Control Compound of the invention (Example 15)
    Untreated 0.0001% 0.001% 0.01% 0.1%
    Stem length, cm 12 15.3 8.0 9.8 12.5
    Number of leaves 2.6 2.6 2.4 2.4 2.8
    Root length, cm 16.8 19.3 4.5 4.5 14.7
    Germination rate, % 100 100 50 50 10
    Table 12
    Effects on the stem length and leaves number and root length of the rice plant
    Control Compound of the invention (Example 15)
    Untreated 0.0001% 0.001% 0.01% 0.1%
    Stem length, cm 7.4 6.5 7.3 6.6 9.3
    Number of leaves 1.6 1.5 1.5 1.8 1.5
    Root length, cm 11.0 12.0 12.4 7.5 6.1
    • Example 18
  • A four-necked flask fitted with stirrer and condenser means was charged with 40.5 g of oleylmethyl­dihydroxyethylammonium chloride, 14.2 g of an equimolar mixture of potassium diisopropyl phosphate and potas­sium monoisopropyl phosphate and 200 g of isopropyl alcohol and the reaction was conducted at 70-80°C in an atmosphere of nitrogen gas introduced at a low flow rate for 7 hours. The precipitate was then collected by filtration and washed with 30 ml of isobutyl alco­hol. The filtrate and the washings were combined and concentrated under reduced pressure and the residue was dissolved in 200 g of toluene and filtered. Finally, the filtrate was concentrated to give 47.05 g (theo­retical yield 49.09 g) of oleylmethyldihydroxyethyl­ammonium mono/diisopropyl phosphate as a waxy product. The elemental analysis and infrared absorption data are given below.
    Analysis (%; calcd. in parentheses)
    C, 65.18 (65.50)
    H, 11.40 (11.54)
    O, 15.60 (15.67)
    N, 2.95 ( 2.93 )
    P, 4.27 ( 4.33)
    Cl, 0.01
    IR
  • In addition to the absorptions of oleylmethyldi­hydroxyethylammonium, absorptions assignable to -P=O and ROP- were observed at 1220 cm⁻¹ and 1065 cm⁻¹.
    • Example 19
  • A four-necked flask fitted with stirrer and condenser means was charged with 40.5 g of oleylmethyl­dihydroxyethylammonium chloride, 21.5 g of potassium monolaurylethoxyethyl phosphate prepared from lauryl alcohol-ethylene oxide (2 mol) adduct and 150 g of isopropyl alcohol and the reaction was conducted at 75-80°C in an atmosphere of nitrogen gas introduced at a low flow rate for 8 hours. The precipitate was then collected by filtration and washed with 50 ml of isopropyl alcohol. The filtrate and the washings were combined and concentrated under reduced pressure and the residue was dissolved in 200 g of benzene and filtered. The filtrate was then concentrated to give 51.27 g (theoretical yield 54.55 g) of oleylmethyldi­hydroxyethylammonium laurylethoxyethyl phosphate as a waxy product. The elemental analysis is shown below.
    Analysis (%; calcd. in parentheses)
    C, 68.01 (68.13)
    H, 11.78 (11.81)
    O, 14.67 (14.65)
    N, 2.58 ( 2.56)
    P, 2.80 ( 2.83)
    Cl, 0.01
    • Example 20
  • The compound synthesized in Example 18 is dis­solved in water to prepare 0.0001%, 0.001%, 0.01% and 0.1% aqueous solutions and soybean, corn and paddy rice seeds are immersed in the solutions at 25°C for 12 hours. Then, polyethylene cups are filled with vermi­culite and the above seeds are sown. The cups are placed in a green house maintained at an interior temperature of 25°C and kept for 10 days, with daily replenishment of water. As controls, the corresponding seeds soaked in water are similarly grown.
  • Tables 13 to 15 show the predicted mean stem length and leaves number and mean root length of each plant.
  • It is apparent that the compound according to Example 18 has plant growth regulating activity. Table 13
    Effects on the stem length and leaves number and root length of the soybean plant
    Control Compound of the invention (Example 18)
    Untreated 0.0001% 0.001% 0.01% 0.1%
    Stem length, cm 18 22.7 23.9 23.0 22.7
    Number of leaves 7.5 8.3 9.3 11.3 7.9
    Root length, cm 11.0 12.0 12.1 11.6 11.1
    Table 14
    Effects on the stem length and leaves number and root length of the corn plant
    Control Compound of the invention (Example 18)
    Untreated 0.0001% 0.001% 0.01% 0.1%
    Stem length, cm 12 15.9 16.9 17.6 15.6
    Number of leaves 2.6 2.9 3.1 2.6 3.1
    Root length, cm 16.8 18.0 21.0 20.6 19.5
    Table 15
    Effects on the stem length and leaves number and root length of the rice plant
    Control Compound of the invention (Example 18)
    Untreated 0.0001% 0.001% 0.01% 0.1%
    Stem length, cm 7.4 9.5 10.2 8.9 10.2
    Number of leaves 1.6 2.4 2.6 2.2 2.4
    Root length, cm 11.0 12.9 14.4 12.1 13.0

Claims (15)

1. An oxyalkylated quaternary ammonium compound consisting of a cationic group of the following general formula and an anionic group selected from the class consisting of carboxylic acid residues, aminosulfonic acid residues and phosphoric acid ester residues.
Figure imgb0017
 wherein R₁ means an C₆₋₂₂ alkyl or alkenyl group, R₂ means an C₁₋₄ alkyl or hydroxyalkyl group and R₃ and R₄ independently mean (BO)xH where B is an C₁₋₄ alkylene group and x means a whole or fractional number of 1 to 5.
2. The oxyalkylated quaternary ammonium compound of claim 1 which has the general formula
Figure imgb0018
 wherein R₁, R₂, R₃ and R₄ are respectively as defined in claim 1, A⊖ is R₅NHR₆COO⊖,
Figure imgb0019
 where R₅ means a hydrogen atom, an C₁₋₄ alkyl group,
Figure imgb0020
 NH₂CH₂(CH₂)₃-, or HSCH₂-, and R₆ means CH, CH₂ or an aromatic group.
3. The oxyalkylated quaternary ammonium compound of claim 1 which has the general formula
Figure imgb0021
 wherein R₁, R₂, R₃ and R₄ are respectively as defined in claim 1, m means 2 or 3, and E means an C₁₋₁₀ alkyl group, an alkylene group, a hydroxyalkyl group, a sulfur-containing alkyl group, an aminoalkyl group or a sulfur-containing aminoalkyl group or the absence of such a group.
4. The oxyalkylated quaternary ammonium compound of claim 1 which has the general formula
Figure imgb0022
 wherein R₁, R₂, R₃ and R₄ are respectively as defined in claim 1, R₇ means a hydrogen atom or an C₁₋₆ alkyl group, and R₈ means an C₁₋₆ alkylene group or an aromatic group.
5. The oxyalkylated quaternary ammonium compound of claim 1 which has the general formula
Figure imgb0023
 wherein R₁, R₂, R₃ and R₄ are respectively as defined in claim 1 and R₉ means a hydrogen atom, a saturated or unsaturated C₁₋₂₂ alkyl group, a hydroxyalkyl group, an alkylene group, a mercaptoalkyl group, an aromatic group, an aromatic group-substituted alkyl group, a hydroxy-containing aromatic group, an alkyl­aryl group,
Figure imgb0024
 CH₃CO-, or CH₃COCH₂-.
6. The oxyalkylated quaternary ammonium compound of claim 1 which has the general formula
Figure imgb0025
 wherein R₁, R₂, R₃ and R₄ are respectively as defined in claim 1, n means 1 or 2, and R₁₀ means a straight-chain or branched C₁₋₂₂ alkyl group, an C₁₋₂₂ alkyl-containing alkoxypolyethoxyethyl group, an C₁₋₂₂ alkyl-containing alkylphenoxypolyethoxyethyl group, or a mono-, di- or tristyrylphenoxypolyethoxy­ethyl group, and when there exist two R10's, they may be the same or different.
7. A process for producing the oxyalkylated quater­nary ammonium compound of claim 1 which comprises reacting a quaternary ammonium compound of the general formula
Figure imgb0026
 wherein R₁, R₂, R₃ and R₄ are respectively as defined in claim 1 and Y means Cl, Br, I or F with at least one member of the class consisting of alkali metal salts of carboxylic acids, alkaline earth metal salts of carboxylic acids, alkali metal salts of aminosulfonic acids, alkaline earth metal salts of aminosulfonic acids, alkali metal salts of phosphoric acid esters and alkaline earth metal salts of phospho­ric acid esters in a solvent, either in the presence of a small amount of the oxyalkylated quaternary ammonium compound of claim 1 or in the absence thereof.
8. A process for producing the oxyalkylated quater­nary ammonium compound of claim 2 which comprises reacting a quaternary ammonium compound of the general formula
Figure imgb0027
 wherein R₁, R₂, R₃ and R₄ are respectively as defined in claim 1 and Y is as defined in claim 7 with a compound of the general formula
R₅NH₆COOD,
a compound of the general formula
Figure imgb0028
 a compound of the general formula
Figure imgb0029
 wherein R₅ and R₆ are as defined in claim 2 and D means an alkali metal atom or an alkaline earth metal atom in a solvent, either in the presence of a small amount of the oxyalkylated quaternary ammonium compound of claim 2 or in the absence thereof.
9. A process for producing the oxyalkylated quater­nary ammonium compound of claim 3 which comprises reacting a quaternary ammonium compound of the general formula
Figure imgb0030
 wherein R₁, R₂, R₃ and R₄ are respectively as defined in claim 1 and Y is as defined in claim 7 with a compound of the general formula
E(COOD)m
wherein E, D and m are as defined in claim 3 or 8 in a solvent, either in the presence of a small amount of the oxyalkylated quaternary ammonium compound of claim 3 or in the absence thereof.
10. A process for producing the oxyalkylated quater­nary ammonium compound of claim 4 which comprises reacting a quaternary ammonium compound of the general formula
Figure imgb0031
 wherein R₁, R₂, R₃ and R₄ are respectively as defined in claim 1 and Y is as defined in claim 7 with a compound of the general formula
R₇NHR₈SO₃D
wherein R₇, R₈ and D are as defined in claim 4 or 8 in a solvent, either in the presence of a small amount of the oxyalkylated quaternary ammonium compound of claim 4 or in the absence thereof.
11. A process for producing the oxyalkylated quater­nary ammonium compound of claim 5 which comprises reacting a quaternary ammonium compound of the general formula
Figure imgb0032
 wherein R₁, R₂, R₃ and R₄ are respectively as defined in claim 1 and Y is as defined in claim 7 with a compound of the general formula
R₉COOD
wherein R₉ and D are as defined in claim 5 or 8 in a solvent, either in the presence of a small amount of the oxyalkylated quaternary ammonium compound of claim 5 or in the absence thereof.
12. A process for producing the oxyalkylated quater­nary ammonium compound of claim 6 which comprises reacting a quaternary ammonium compound of the general formula
Figure imgb0033
 wherein R₁, R₂, R₃ and R₄ are respectively as defined in claim 1 and Y is as defined in claim 7 with a compound of the general formula

(R₁₀O)3-n
Figure imgb0034
(OD)n
wherein R₁₀, n and D are as defined in claim 6 or 8 in a solvent, either in the presence of a small amount of the oxyalkylated quaternary ammonium compound of claim 6 or in the absence thereof.
13. The process claimed in any of claims 7, 8, 9, 10, 11 and 12 wherein said solvent is at least a member selected from the class consisting of straight-chain or branched C₁₋₆ alcohols, methyl ethyl ketone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, dioxane, ethyl acetate and cyclohexanol, and these solvents may be used singly or in combination.
14. A plant growth regulating composition which comprises an oxyalkylated quaternary ammonium compound claimed in claim 1 as an active ingredient.
15. The plant growth regulating composition of claim 14 which is used in the form of an aqueous solution.
EP89121723A 1988-11-28 1989-11-24 Oxyalkylated quaternary ammonium compounds, processes for production thereof, and plant growth regulating compositions containing said compounds Expired - Lifetime EP0371406B1 (en)

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JP30147688A JPH02145552A (en) 1988-11-28 1988-11-28 Novel quaternary ammonium compound, production thereof and plant growth regulator containing the same as active ingredient
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994002021A1 (en) * 1992-07-16 1994-02-03 Monsanto Company Herbicidal compositions
US5561187A (en) * 1991-11-01 1996-10-01 Witco Corporation Cationic polyurethane compositions, quaternary ammonium salts and methods for their preparation
CN102643204A (en) * 2012-04-11 2012-08-22 深圳市美凯特科技有限公司 Trihydroxyethyl quaternary ammonium salt and preparation method thereof
CN103936600A (en) * 2014-04-16 2014-07-23 天津大学 Method for purifying cationic etherifying agent via phosphate ester extraction agent

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5525261A (en) * 1994-10-18 1996-06-11 Henkel Corporation Anti-static composition and method of making the same
ATE214653T1 (en) * 1996-05-28 2002-04-15 Lonza Ag WOOD PRESERVATIVE
US8207089B1 (en) * 2010-02-26 2012-06-26 Plant Food Systems, Inc. Concentrated compositions that provide disease and pest control to plants

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3661945A (en) * 1970-03-27 1972-05-09 Hans S Mannheimer Reaction products of certain cationic compounds with anionic compounds,compositions containing same and methods for preparing same
GB1479708A (en) * 1976-02-27 1977-07-13 Wilkinson Sword Ltd Aerosol foams
EP0146017A1 (en) * 1983-11-26 1985-06-26 Mitsubishi Gas Chemical Company, Inc. Plant growth regulator and method for increasing crop yields and promoting root formation
EP0241223A2 (en) * 1986-04-07 1987-10-14 Kao Corporation Electrographic toner and process for preparation thereof
WO1988006655A2 (en) * 1987-02-25 1988-09-07 Kao Corporation Non-aqueous shade enhancing agent

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3661945A (en) * 1970-03-27 1972-05-09 Hans S Mannheimer Reaction products of certain cationic compounds with anionic compounds,compositions containing same and methods for preparing same
GB1479708A (en) * 1976-02-27 1977-07-13 Wilkinson Sword Ltd Aerosol foams
EP0146017A1 (en) * 1983-11-26 1985-06-26 Mitsubishi Gas Chemical Company, Inc. Plant growth regulator and method for increasing crop yields and promoting root formation
EP0241223A2 (en) * 1986-04-07 1987-10-14 Kao Corporation Electrographic toner and process for preparation thereof
WO1988006655A2 (en) * 1987-02-25 1988-09-07 Kao Corporation Non-aqueous shade enhancing agent

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 103, no. 10, 8th August 1985, page 144, abstract no. 73677f, Columbus, Ohio, US; JP-A-60 02 357 (ASAHI DENKA KOGYO K.K.) 21-01-1985, & QUESTEL DARC On-line Graphic of compound no. 97586-89-5 *
CHEMICAL ABSTRACTS, vol. 106, no. 22, 1st June 1987, page 84, abstract no. 178069z, Columbus, Ohio, US; & JP-A-61 252 370 (TAKEMOTO OIL & FAT CO., LTD) 10-11-1986, & QUESTEL DARC On-line Graphic of compound no. 107889-14-5 *
CHEMICAL ABSTRACTS, vol. 108, no. 2, 11th January 1988, page 267, abstract no. 10328a, Columbus, Ohio, US; & JP-A-62 110 999 (KURARAY CO. LTD) 22-05-1987, & QUESTEL DARC On-line Graphic of comound no. 111944-78-6 *
CHEMICAL ABSTRACTS, vol. 109, no. 15, 10 October 1988, page 254, abstract no. 124403x, Columbus, Ohio, US; & JP-A-63 64 701 (KAO CORP.) 23-03-1988, & QUESTEL DARC On-line Graphic of compound no. 116329-54-5 *
CHEMICAL ABSTRACTS, vol. 109, no. 9, 29th August 1988, page 648, abstract no. 73006k, Columbus, Ohio, US; JP-A-63 60 953 (DAIICHI KOGYO SEIYAKU CO., LTD) 17-03-1988 *
CHEMICAL ABSTRACTS, vol. 83, no. 10, 8th September 1975, page 112, abstract no. 81147s, Columbus, Ohio, US; JP-A-75 23 383 (DAIKIN KOGYO CO., LTD) 13-03-1975, & QUESTEL DARC On-line Graphic of compounds no. 55987-26-3 *
CHEMICAL ABSTRACTS, vol. 98, no. 6, 7th February 1983, page 13, abstract no. 35136z, Columbus, Ohio, US; & JP-A-57 117 520 (ASAHI CHEMICAL IND. CO., LTD) 20-07-1982, & QUESTEL DARC On-line Graphic of compound no. 84164-97-6 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5561187A (en) * 1991-11-01 1996-10-01 Witco Corporation Cationic polyurethane compositions, quaternary ammonium salts and methods for their preparation
EP0541289B1 (en) * 1991-11-01 1997-03-12 Witco Corporation Methods for the preparation of cationic polyurethane compositions and quaternary ammonium salts
WO1994002021A1 (en) * 1992-07-16 1994-02-03 Monsanto Company Herbicidal compositions
CN102643204A (en) * 2012-04-11 2012-08-22 深圳市美凯特科技有限公司 Trihydroxyethyl quaternary ammonium salt and preparation method thereof
CN103936600A (en) * 2014-04-16 2014-07-23 天津大学 Method for purifying cationic etherifying agent via phosphate ester extraction agent
CN103936600B (en) * 2014-04-16 2016-08-24 天津大学 Phosphoric acid ester extractant purifies the method for cationic etherifying agent

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EP0371406B1 (en) 1993-08-04
DE68908105D1 (en) 1993-09-09

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